EP0062079B1 - Thin silicon film and process for preparing same - Google Patents
Thin silicon film and process for preparing same Download PDFInfo
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- EP0062079B1 EP0062079B1 EP81902820A EP81902820A EP0062079B1 EP 0062079 B1 EP0062079 B1 EP 0062079B1 EP 81902820 A EP81902820 A EP 81902820A EP 81902820 A EP81902820 A EP 81902820A EP 0062079 B1 EP0062079 B1 EP 0062079B1
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- film
- silicon thin
- gas
- thin film
- silicon
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims description 55
- 229910052710 silicon Inorganic materials 0.000 title claims description 53
- 239000010703 silicon Substances 0.000 title claims description 53
- 238000004519 manufacturing process Methods 0.000 title description 3
- 239000010408 film Substances 0.000 claims description 67
- 239000010409 thin film Substances 0.000 claims description 58
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 31
- 239000007789 gas Substances 0.000 claims description 26
- 230000003287 optical effect Effects 0.000 claims description 20
- 229910000077 silane Inorganic materials 0.000 claims description 20
- 239000002019 doping agent Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 9
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 230000000737 periodic effect Effects 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052785 arsenic Inorganic materials 0.000 claims description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910021424 microcrystalline silicon Inorganic materials 0.000 claims description 2
- 150000004756 silanes Chemical class 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 2
- 229910021419 crystalline silicon Inorganic materials 0.000 claims 1
- 230000008021 deposition Effects 0.000 claims 1
- 229910021478 group 5 element Inorganic materials 0.000 claims 1
- 229910052754 neon Inorganic materials 0.000 claims 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims 1
- 238000007796 conventional method Methods 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 229910016523 CuKa Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- UJKWLAZYSLJTKA-UHFFFAOYSA-N edma Chemical compound O1CCOC2=CC(CC(C)NC)=CC=C21 UJKWLAZYSLJTKA-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Images
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
- H10D62/00—Semiconductor bodies, or regions thereof, of devices having potential barriers
- H10D62/40—Crystalline structures
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/24—Deposition of silicon only
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/0237—Materials
- H01L21/02422—Non-crystalline insulating materials, e.g. glass, polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02524—Group 14 semiconducting materials
- H01L21/02532—Silicon, silicon germanium, germanium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/0257—Doping during depositing
- H01L21/02573—Conductivity type
- H01L21/02579—P-type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02587—Structure
- H01L21/0259—Microstructure
- H01L21/02592—Microstructure amorphous
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
- H10D62/00—Semiconductor bodies, or regions thereof, of devices having potential barriers
- H10D62/80—Semiconductor bodies, or regions thereof, of devices having potential barriers characterised by the materials
- H10D62/83—Semiconductor bodies, or regions thereof, of devices having potential barriers characterised by the materials being Group IV materials, e.g. B-doped Si or undoped Ge
- H10D62/834—Semiconductor bodies, or regions thereof, of devices having potential barriers characterised by the materials being Group IV materials, e.g. B-doped Si or undoped Ge further characterised by the dopants
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- H10F71/00—Manufacture or treatment of devices covered by this subclass
- H10F71/10—Manufacture or treatment of devices covered by this subclass the devices comprising amorphous semiconductor material
- H10F71/103—Manufacture or treatment of devices covered by this subclass the devices comprising amorphous semiconductor material including only Group IV materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12528—Semiconductor component
Definitions
- This invention relates to a silicon thin film and a method of producing the same, and particularly, to a low resistance silicon thin film which is formed on an appropriate substrate in a plasma atmosphere, and a method of producing the same.
- a silicon thin film on an appropriate substrate in a plasma atmosphere, using as a raw material a mixture of silane SiH 4 and a dopant material.
- the conventional silicon thin film produced by such method is entirely amorphous.
- the amorphous film produces a halo pattern in the X-ray diffraction, and such amorphous silicon thin film has an electrical conductivity of at most about 10- 2 0-1 c m - 1 for the N type and about 10- 3 0- 1 cm- 1 for the P type.
- the activation energy which is estimated on the basis of the temperature dependence of the electrical conductivity is rather high, that is, about 0.2 eV both for P type and N type films.
- the amorphous thin film is a P + or N' type film which has a good ohmic contact to metal and in which the Fermi level is adequately degenerated (for example, see the Philosophical Magazine, 33, p. 935,1976).
- the P type film as the electrical conductivity becomes higher, the optical band gap is sharply reduced (see the Physical Review, 19, p. 2041, 1979).
- polycrystalline thin films which are produced of silane SiH 4 as by a chemical vapor deposition have higher electrical conductivities, they have optical band gaps as low as 1.2 eV, which is not adequate to the solar spectrum. Further, the grain boundaries between crystals not only act as recombination centers of electron-hole pairs, but also contribute to the leakage of current.
- Other objects of the invention are to provide a P type silicon thin film having a high electrical conductivity, a wide band gap, and an excellent doping effect, and to provide a N type silicon thin film, having a high electrical conductivity and an excellent doping effect.
- a silicon thin film composed of primarily silicon atoms, characterised in that said film comprises a dispersion of microcrystalline silicon grains in amorphous silicon, said microcrystalline grains having an average grain diameter in the range of 3 nm to 50 nm and the microcrystalline grains being present in the film in an amount by volume of 20 to 80%.
- amorphous silicon thin films which were prepared under a plasma atmosphere exhibit a halo pattern devoid of any sharp peak
- polycrystalline silicon thin films which were prepared by chemical vapor deposition, high temperature annealing, etc. exhibit a clear and intensive peak which is derived from the silicon crystal lattice.
- the silicon thin films according to this invention show a weak peak near Si(111) or Si(220) on the halo pattern, which is presumably derived from the silicon crystal lattice.
- the average diameter of the microcrystalline grains in the silicon thin film according to this invention can be calculated from the half-value width of the above mentioned peak using the Scherrer equation and, as aforesaid, it ranges from about 3 nm to about 50 nm.
- the microcrystalline substance in this range of grain diameters does not provide any optical barrier in the range of wave lengths involved in the solar radiation, and can only cause the electrical conductivity to increase. It is deduced that if the microcrystalline substance has an average grain diameter below about 3 nm, it will hardly continue to exist and will tend to lose its crystalline characteristics, thus approaching the amorphous state.
- the microcrystalline substance has an average grain diameter over about 50 nm, it will tend to change into a polycrystalline condition, so that an interference of light at the boundary between the amorphous layer and the crystalline grains will occur. It would then be impossible to lower the electrical resistance without narrowing down the optical band gap.
- the most desirable range of average grain diameter for the silicon thin film to have a low electrical resistance and a wide optical band gap is about 5 nm to about 20 nm.
- the proportion of the microcrystalline substance in the amorphous substance can be estimated from the X-ray diffraction pattern on the basis of the height of peak and the half-value width, and it is about 20 percent by volume to about 80 percent by volume.
- the proportion of the microcrystalline substance is below about 20 percent by volume, the electrical characteristic of the silicon thin film becomes similar to that of the amorphous film and the effect due to the dispersion of the crystalline substance does not appear, and consequently, the objects of this invention cannot be accomplished.
- the existence of the microcrystalline substance over about 80 percent by volume brings forth the disadvantage that the amount of hydrogen in the film is lowered and the optical band gap is narrowed.
- the existence of the microcrystalline substance in the amorphous layer may closely relate to the fact that the film combines the excellent features (a) of an amorphous silicon thin film, i.e. the adequately wide optical band gap, and (b) of a polycrystalline silicon thin film, i.e. the remarkably high electrical conductivity.
- various elements can be used as an impurity dopant.
- elements in the Group V of the Periodic Table such as phosphorus, arsenic, etc.
- silicon thin films having a property of N type semiconductor are obtained, while the use of elements in the Group III of the Periodic Table, such as boron, aluminium, etc. will provide a silicon thin film having a property of P type semiconductor.
- the former films are characterized by the electrical conductivity of about 10- 1 ⁇ -1 cm -1 to about 10 0 (2-'cm-', while the latter films are characterized by that of about 10 -2 ⁇ -1 cm -1 to about 10 -1 ⁇ -1 cm -1 .
- silicon thin films having N type or P type property which are characterized by the activation energy on the basis of the electrical conductivity below about 0.2 eV, often below about 0.1 eV, a good doping effect, an adequately degenerated Fermi level, and an excellent ohmic contact to metal.
- the silicon thin films according to this invention either of a N type or P type, can maintain an adequately wide optical band gap even by added doping, and they have a considerably higher value of about 1.3 eV to about 1.8 eV in comparison with the value of about 1.2 of the polycrystalline films.
- the P type thin films especially have two excellent characteristics, i.e. high electrical conductivity and wide optical band gap, which could not have been obtained in conventional films.
- any one of silane SiH 4 or halogenated silane SiH o - 3 X 4 - 1 (X represents a halogen element), or a gas mixture including two or more of these gases is diluted with a rare gas such as helium, argon, etc. or a hydrogen gas in a ratio higher than 1:1, and then a dopant gas is added to the diluted gas mixture.
- a rare gas such as helium, argon, etc. or a hydrogen gas in a ratio higher than 1:1
- a dopant gas is added to the diluted gas mixture.
- the invention is not limited to this particular sequence of mixing and dilution.
- Electrical energy having a plasma discharge power density higher than about 0.2 W/cm 2 is applied to the gas mixture to produce a plasma condition, in which a film is formed on a substrate (consisting of glass, plastic, metal, etc.). Then, the impurity atoms as dopant are efficiently incorporated into a silicon network with four coordinations, so that a silicon thin film having a high electrical conductivity can be formed without narrowing down the optical band gap.
- the purpose for which the silane SiH 4 is diluted with hydrogen or rare gas is to control the film forming rate under the applied high electrical energy.
- the silane is diluted with hydrogen or rare gas to suppress the film forming rate in the application of high electric power (preferably, below 0.4 nm/sec).
- the X-ray diffraction pattern from the film which has been produced under such condition shows that micro-crystalline grains are interspersed in the amorphous substance, and it is deduced that the existence of such microcrystalline grains remarkably reduces the resistance of the film without detracting from the optical property characteristic of amorphous films.
- the whole system including a mixing chamber 1 is evacuated to a degree of vacuum of about 10- 6 torr (0.133 mPa) using a rotary oil pump 2 and an oil diffusion pump 3, and gases are introduced from a silane source 4, a hydrogen source 5, and from a dopant gas source 6 or 7 as required, to the mixing chamber 1 in a required proportion and are mixed there.
- the gas mixture is supplied through a flow rate meter 8 to an evacuated chamber 9 at a predetermined flow rate.
- the pressure or degree of vacuum within the chamber 9 is maintained at a required value by manipulating a main valve 10 while observing a vacuum meter 11.
- a high frequency voltage is applied across electrodes 13 and 13' to produce a glow discharge.
- a substrate 15 is placed on a base plate which is heated by a heater 14 to a required temperature.
- a doped, hydrogenated silicon thin film is produced on the substrate 15.
- Table I illustrates examples of the method of producing film according to this invention and the characteristics of the formed films in comparison with the conventional methods and films.
- the samples designated by Nos. 1 to 3 are P type silicon thin films which were prepared by the conventional method, the film forming conditions and film characteristics thereof being given in the Table.
- the samples designated by Nos. 4 and 5 are P type silicon thin films which were prepared using this invention.
- the silane SiH 4 was diluted with hydrogen at a ratio of silane to hydrogen of 1:30 and high electric powers of 0.8W/cm 2 and 1.6W/cm 2 , respectively were applied.
- the samples designated by Nos. 6 to 9 and No. 11 are N type silicon thin films which were prepared by the conventional method, while the samples designated by Nos.
- 10 and 12 are N type silicon thin films which were prepared by this invention.
- the silane was diluted with hydrogen at a ratio of silane to hydrogen of 1 to 10 and electrical powers of 0.8W/cm 2 and 1.6W/cm 2 , respectively were applied.
- the Table II illustrates other examples of the method of producing silicon thin film according to this invention and the characteristics of the formed films.
- the sample designated by No. 13 is P type silicon thin film which was prepared according to this invention and the film forming conditions and film characteristics thereof are given in the Table.
- the silane SiH 4 was diluted by argon at a ratio of silane to argon of 1:30, high electric power of 1.5 W/cm 2 was applied, and a mixed gas of B 2 H 6 /SiH 4 of 20,000 ppm by vol. was used as a dopant.
- the sample designated by No. 14 is N type silicon thin film which was also prepared according to this invention and there are described firm forming conditions and film characteristics thereof.
- the samples designated by No. 15 and 16 are I layers which were prepared according to this invention. They were formed by diluting the silane SiH 4 with argon at a high proportion and applying high electric power.
- Fig. 2 is a graph showing the electrical conductivity of the silicon thin films as a function of the concentration of dopant gas.
- the curves 16 and 17 show the electrical conductivity of the P type and N type silicon thin films, respectively, produced by the conventional method, in which the films were formed at a cathode plasma discharge power density (fed plasma discharge power/area of cathode electrode) of about 0.1 W/cm 2 .
- the points 18 and 19 shows the electrical conductivity of the P type silicon thin films produced by the method of this invention, in which the silane SiH 4 was diluted with hydrogen at ratio of silane to hydrogen of 1:30, and 2% by volume of diborane B 2 H 6 to silane was added to the gas mixture while plasma discharge power densities of 0.8W/cm 2 and 1.6W/cm 2 , respectively were employed.
- FIG. 2 shows the conductivity of the N type silicon thin films produced by the method of this invention, in which silane was diluted with hydrogen at a ratio of silane to hydrogen of 1:10, and for the point 20, 1 % by volume of phosphorus pentafluoride PF S , and for the point 21, 4500 ppm by volume of phosphine PH 3 were added while power densities of 0.8W/cm 2 and 1.6W/cm 2 , respectively were used.
- Fig. 2 shows that the conductivity of silicon thin films made according to this invention is increased at least by two orders of magnitude in comparison with films produced by the conventional method.
- Fig. 3 shows the activation energy on the basis of the electrical conductivity of silicon thin films as a function of the concentration of dopant gas.
- the curves 22 and 23 in Fig. 3 represent the activation energy of the films produced by the conventional method, for which the film forming conditions corresponding to the curves 16 and 17 in Fig. 2 were used, respectively.
- the points 24, 25, 26 and 27 represent the activation energy of the films produced by this invention, in which the film forming conditions described in relation to points 18,19,20 and 21 of Fig. 2 were used, respectively.
- Fig. 3 substantiates that this invention provides a p + type or N type film having a low activation energy on the basis of electrical conductivity, a good ohmic contact to metal, and an adequately degenerated Fermi level.
- Fig. 4 is a graph showing the concentrations of boron and phosphorus in silicon thin films as a function of the concentration of dopant gas, as measured by the SIMS and EDMA methods.
- the curves 28 and 29 represent the films produced by the conventional method, in which the film forming conditions corresponding to the curves 16 and 17 in Fig. 2 were used.
- the points 30, 31, 32 and 33 in Fig. 4 represent the films produced by the method of this invention, in which the film forming conditions described in relation to points 18, 19, 20 and 21 in Fig. 2 were used, respectively.
- Fig. 5 shows the optical band gap of the P type silicon thin film as a function of the concentration of dopant gas.
- the optical band gap is calculated on the basis of wherein a represents the absorption coefficient, hy the incident photon energy (eV), and E o , the optical band gap.
- the curve 34 in Fig. 5 relates to the film produced by the conventional method, in which the film forming conditions were as described for the curve 16 in Fig. 2 were used. It shows that as the concentration of boron increases, the optical band gap decreases.
- the points 35 and 36 are for the silicon films of this invention, in which the film forming condition as described for the points 18 and 19 in Fig. 2 were employed, respectively.
- Fig. 5 shows that the P type silicon thin film of this invention has a high electrical conductivity without the optical band gap being narrowed.
- Fig. 6 shows an example of X-ray (CuKa) diffraction pattern of silicon thin films (having a film thickness of 111m).
- the curve 37 in Fig. 6 is a representative example of the sample of the invention, in which peaks are observed near Si (111) and Si (220). The grain diameter is calculated from the half-value width of peak to be about 10 nm.
- the curve 38 in Fig. 6 represents the silicon thin film produced by the conventional method, in which no peak is observed unlike the curve 37. Further, the halo pattern appearing in this Figure is due to the glass material as a substrate, and halo pattern from the amorphous silicon film is not clearly observed, since the film is thin.
- a P type and N type silicon thin film having a high doping effect and a high electrical conductivity which have a wide application.
- P type silicon thin film is useful for solar cells and the like, since it can provide a high electrical conductivity without the optical band gap being narrowed.
- this invention has great advantages when used in the electric industries.
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- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Photovoltaic Devices (AREA)
- Silicon Compounds (AREA)
- Chemical Vapour Deposition (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP143010/80 | 1980-10-15 | ||
JP55143010A JPS5767020A (en) | 1980-10-15 | 1980-10-15 | Thin silicon film and its manufacture |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0062079A1 EP0062079A1 (en) | 1982-10-13 |
EP0062079A4 EP0062079A4 (en) | 1984-02-16 |
EP0062079B1 true EP0062079B1 (en) | 1986-09-03 |
Family
ID=15328842
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP81902820A Expired EP0062079B1 (en) | 1980-10-15 | 1981-10-15 | Thin silicon film and process for preparing same |
Country Status (5)
Country | Link |
---|---|
US (1) | US5017308A (enrdf_load_stackoverflow) |
EP (1) | EP0062079B1 (enrdf_load_stackoverflow) |
JP (1) | JPS5767020A (enrdf_load_stackoverflow) |
CA (1) | CA1175583A (enrdf_load_stackoverflow) |
WO (1) | WO1982001441A1 (enrdf_load_stackoverflow) |
Families Citing this family (37)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5939713A (ja) * | 1982-08-29 | 1984-03-05 | Agency Of Ind Science & Technol | シリコン薄膜及びその製造方法 |
EP0153043A3 (en) * | 1984-02-15 | 1986-09-24 | Energy Conversion Devices, Inc. | Ohmic contact layer |
JPS60200523A (ja) * | 1984-03-26 | 1985-10-11 | Agency Of Ind Science & Technol | シリコン薄膜の製造法 |
US4609771A (en) * | 1984-11-02 | 1986-09-02 | Sovonics Solar Systems | Tandem junction solar cell devices incorporating improved microcrystalline p-doped semiconductor alloy material |
JPS61214475A (ja) * | 1985-03-19 | 1986-09-24 | Agency Of Ind Science & Technol | 薄膜トランジスタ |
CA1335950C (en) * | 1986-10-03 | 1995-06-20 | Kenneth George Sharp | Method of forming semiconducting amorphous silicon films from the thermal decomposition of dihalosilanes |
JPH0637703B2 (ja) * | 1986-12-22 | 1994-05-18 | 三井東圧化学株式会社 | 半導体薄膜の製法 |
JP2516964B2 (ja) * | 1987-03-31 | 1996-07-24 | 鐘淵化学工業株式会社 | 歪センサ− |
US4937550A (en) * | 1987-03-31 | 1990-06-26 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Strain sensor |
JPH0351971Y2 (enrdf_load_stackoverflow) * | 1988-05-12 | 1991-11-08 | ||
NL8801379A (nl) * | 1988-05-30 | 1989-12-18 | Imec Inter Uni Micro Electr | Werkwijze voor het vervaardigen van een dunne-filmtransistor en een dergelijke dunne-filmtransistor. |
JP2679354B2 (ja) * | 1990-04-13 | 1997-11-19 | 松下電器産業株式会社 | 非線形光学材料およびその製造方法 |
US8106867B2 (en) | 1990-11-26 | 2012-01-31 | Semiconductor Energy Laboratory Co., Ltd. | Electro-optical device and driving method for the same |
US7154147B1 (en) * | 1990-11-26 | 2006-12-26 | Semiconductor Energy Laboratory Co., Ltd. | Electro-optical device and driving method for the same |
JPH04299578A (ja) * | 1991-03-27 | 1992-10-22 | Canon Inc | 光電変換素子及び薄膜半導体装置 |
WO1993017449A1 (en) * | 1992-02-25 | 1993-09-02 | Energy Conversion Devices, Inc. | Semiconductor with ordered clusters and laser ablation method for the fabrication thereof |
US5776819A (en) * | 1992-05-05 | 1998-07-07 | Midwest Research Institute | Deposition of device quality, low hydrogen content, amorphous silicon films by hot filament technique using "safe" silicon source gas |
US6078059A (en) * | 1992-07-10 | 2000-06-20 | Sharp Kabushiki Kaisha | Fabrication of a thin film transistor and production of a liquid display apparatus |
JPH0697070A (ja) * | 1992-09-11 | 1994-04-08 | Sanyo Electric Co Ltd | 多結晶シリコン膜の製造方法 |
EP0592227A3 (en) * | 1992-10-07 | 1995-01-11 | Sharp Kk | Manufacture of a thin film transistor and production of a liquid crystal display device. |
US5796116A (en) | 1994-07-27 | 1998-08-18 | Sharp Kabushiki Kaisha | Thin-film semiconductor device including a semiconductor film with high field-effect mobility |
US5677236A (en) * | 1995-02-24 | 1997-10-14 | Mitsui Toatsu Chemicals, Inc. | Process for forming a thin microcrystalline silicon semiconductor film |
US5885884A (en) * | 1995-09-29 | 1999-03-23 | Intel Corporation | Process for fabricating a microcrystalline silicon structure |
US6239453B1 (en) | 1996-06-19 | 2001-05-29 | Matsushita Electric Industrial Co., Ltd. | Optoelectronic material, device using the same, and method for manufacturing optoelectronic material |
US6087580A (en) * | 1996-12-12 | 2000-07-11 | Energy Conversion Devices, Inc. | Semiconductor having large volume fraction of intermediate range order material |
KR100652909B1 (ko) * | 1998-03-06 | 2006-12-01 | 에이에스엠 아메리카, 인코포레이티드 | 하이 스텝 커버리지를 갖는 실리콘 증착 방법 |
JP2000077402A (ja) * | 1998-09-02 | 2000-03-14 | Tokyo Electron Ltd | プラズマ処理方法および半導体装置 |
JP4450126B2 (ja) * | 2000-01-21 | 2010-04-14 | 日新電機株式会社 | シリコン系結晶薄膜の形成方法 |
US20040007733A1 (en) * | 2002-06-26 | 2004-01-15 | Macronix International Co., Ltd. | Floating gate memory cell and forming method |
US20040209467A1 (en) * | 2003-04-21 | 2004-10-21 | Sinclair Wang | Method for reducing plasma related damages |
US6872972B2 (en) * | 2003-07-16 | 2005-03-29 | Macronix International Co., Ltd. | Method for forming silicon film with changing grain size by thermal process |
JP4489750B2 (ja) * | 2006-12-06 | 2010-06-23 | 株式会社半導体エネルギー研究所 | シリコン膜の作製方法、半導体装置の作製方法及び光電変換装置の作製方法 |
US8535760B2 (en) * | 2009-09-11 | 2013-09-17 | Air Products And Chemicals, Inc. | Additives to silane for thin film silicon photovoltaic devices |
US8884297B2 (en) * | 2010-05-14 | 2014-11-11 | Semiconductor Energy Laboratory Co., Ltd. | Microcrystalline silicon film, manufacturing method thereof, semiconductor device, and manufacturing method thereof |
US9837271B2 (en) | 2014-07-18 | 2017-12-05 | Asm Ip Holding B.V. | Process for forming silicon-filled openings with a reduced occurrence of voids |
US9443730B2 (en) | 2014-07-18 | 2016-09-13 | Asm Ip Holding B.V. | Process for forming silicon-filled openings with a reduced occurrence of voids |
US10460932B2 (en) | 2017-03-31 | 2019-10-29 | Asm Ip Holding B.V. | Semiconductor device with amorphous silicon filled gaps and methods for forming |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2508802A1 (de) * | 1975-02-28 | 1976-09-09 | Siemens Ag | Verfahren zum abscheiden von elementarem silicium |
US4226898A (en) * | 1978-03-16 | 1980-10-07 | Energy Conversion Devices, Inc. | Amorphous semiconductors equivalent to crystalline semiconductors produced by a glow discharge process |
JPS56122123A (en) * | 1980-03-03 | 1981-09-25 | Shunpei Yamazaki | Semiamorphous semiconductor |
JPS57160174A (en) * | 1981-03-30 | 1982-10-02 | Hitachi Ltd | Thin film solar battery |
-
1980
- 1980-10-15 JP JP55143010A patent/JPS5767020A/ja active Granted
-
1981
- 1981-10-14 CA CA000387901A patent/CA1175583A/en not_active Expired
- 1981-10-15 EP EP81902820A patent/EP0062079B1/en not_active Expired
- 1981-10-15 WO PCT/JP1981/000286 patent/WO1982001441A1/ja active IP Right Grant
-
1989
- 1989-07-11 US US07/377,985 patent/US5017308A/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
EP0062079A1 (en) | 1982-10-13 |
US5017308A (en) | 1991-05-21 |
CA1175583A (en) | 1984-10-02 |
JPS6356172B2 (enrdf_load_stackoverflow) | 1988-11-07 |
WO1982001441A1 (fr) | 1982-04-29 |
JPS5767020A (en) | 1982-04-23 |
EP0062079A4 (en) | 1984-02-16 |
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